EP4219411A1 - Procédé et système pour la récupération de phosphate d'un effluent - Google Patents
Procédé et système pour la récupération de phosphate d'un effluent Download PDFInfo
- Publication number
- EP4219411A1 EP4219411A1 EP23166436.8A EP23166436A EP4219411A1 EP 4219411 A1 EP4219411 A1 EP 4219411A1 EP 23166436 A EP23166436 A EP 23166436A EP 4219411 A1 EP4219411 A1 EP 4219411A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- vivianite
- structures
- phosphate
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 87
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 75
- 239000010452 phosphate Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000011084 recovery Methods 0.000 title claims abstract description 43
- 235000021317 phosphate Nutrition 0.000 claims abstract description 84
- 239000010802 sludge Substances 0.000 claims abstract description 74
- 150000002505 iron Chemical class 0.000 claims abstract description 25
- 239000002244 precipitate Substances 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 18
- 239000010865 sewage Substances 0.000 claims abstract description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 80
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims description 38
- 239000011574 phosphorus Substances 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005259 measurement Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 9
- 230000005484 gravity Effects 0.000 claims description 8
- 159000000014 iron salts Chemical class 0.000 claims description 8
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 239000010801 sewage sludge Substances 0.000 claims description 5
- 239000005569 Iron sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 238000000926 separation method Methods 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000006148 magnetic separator Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000029087 digestion Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 6
- 210000003608 fece Anatomy 0.000 description 6
- 239000010871 livestock manure Substances 0.000 description 6
- 238000007885 magnetic separation Methods 0.000 description 6
- 229910052567 struvite Inorganic materials 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009294 enhanced biological phosphorus removal Methods 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000004813 Moessbauer spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000020774 essential nutrients Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/305—Preparation from phosphorus-containing compounds by alkaline treatment
- C01B25/306—Preparation from phosphorus-containing compounds by alkaline treatment from phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/481—Treatment of water, waste water, or sewage with magnetic or electric fields using permanent magnets
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5209—Regulation methods for flocculation or precipitation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/18—PO4-P
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Definitions
- the invention relates to a method for recovery of phosphate from a (wet) stream, such as a waste flow.
- a (wet) stream such as a waste flow.
- the method recovers phosphate from sewage or another sludge stream, and/or manure.
- An objective of the present invention is to provide a method for phosphate/phosphorus recovery from a stream that obviates or at least reduces the aforementioned problems and is more effective and/or more efficient as compared to conventional methods.
- Streams may comprise phosphate (PO 4 ) that is the main molecule in the relevant streams that comprises the element Phosphorus (P).
- P element Phosphorus
- a waste water treatment plant contains activated sludge which is contacted with the incoming sewage (after first removing particles by means of a primary clarifier).
- the sludge mainly comprising microbial biomass, grows from the aerobic oxidation of the dissolved or colloidal organics in the sewage.
- an iron-salt is added to the activated sludge and sewage mixture. The formed precipitate will be part of the sludge.
- the sludge is retained in the waste water treatment plant by means of a secondary clarifier-settler.
- the supernatant of this clarifier is the treated water and the settled activated sludge is returned to the aerated tank.
- some of the settled sludge needs to be disposed of. This is the waste activated sludge.
- This waste activated sludge is anaerobically digested to reduce the volume and recovery energy in the form of biogas. During this anaerobic digestion vivianite is formed (partly due to the reduction of Fe(III) to Fe(II)).
- the fraction of the phosphate present as vivianite, after digestion depends on the molar ratio between iron and phosphate in the waste activated sludge, and thus on the amount of iron that was added in the activated sludge plant prior to anaerobic digestion.
- the digested sludge is preferably fed into a magnetic separator to separate the magnetic vivianite-like structures from the rest of the digested sludge (largely organics). It was shown that this enables recovery of phosphate.
- Dosing and/or controlling iron salt to the stream enables forming of precipitates in the stream. More specifically, dosing iron salts to the stream enables forming of vivianite (which is a Fe(II) phosphate mineral: Fe 3 (II) [PO 4 ] 2 ⁇ 8H 2 O) or vivianite like structures. Vivianite like structures includes pure vivianite and also structures including some impurities like magnesium or calcium.
- Dosing and/or controlling is to adjust and/or measure and/or determining the amount of iron salt, where the amount of iron salt is in the range of 0 M to a saturated solution, preferably maintaining a specific ratio. For example one which will be described later.
- phosphate is removed from waste water in sewage treatment plants.
- Fe (III) phosphate precipitates and vivianite like structures is formed.
- anaerobic/anoxic digestion step for example for biogas production during manure/sewage treatment
- all Fe (III) transforms into Fe(II) and vivianite like structures can form.
- these vivianite like structures are effectively formed when oxygen is absent and bacteria are active.
- vivianite formation may occur.
- the vivianite formation is favoured during anaerobic/anoxic digestion.
- the vivianity like structures may constitute a valuable phosphorus source as such.
- the structures are further treated to recover the phosphates from the structures.
- the method further comprises the steps of:
- the phosphate recovery is achieved effectively as more than 60% (and up to 90%) of the initial amount of phosphate in the incoming stream is incorporated into the vivianite like structures.
- This removal is achieved by separating the vivianite like structures from the stream.
- This separation of the vivianite like structures enables removal of the phosphates from the stream.
- this indirectly) obviates or at least reduces the problem associated with eutrophication of effluent receiving surface waters due to the iron dosing.
- the higher Fe dosage may also help to lower phosphate concentrations in the effluent of sewage treatment plants
- the phosphates are recovered from the separated vivianite like structures. This enables recycling of phosphorus. Furthermore, recovery of phosphorus is desired due to the limited availability of phosphorus such that a waste water flow may act as a secondary source of phosphorus, for example. This renders streams such as waste streams, sewage and manure, as an alternative source of phosphorus. This also allows for a circular use of phosphate which is an important component of fertilizers. This improves the sustainability of the global food production that involves phosphorus as an essential nutrient.
- the amount of phosphate into the vivianite like structures is achieved as compared to alternative conventional methods, including struvite precipitation. It is suggested that in the presence of iron vivianite, including its structures, preferably forms over other inorganic phosphate phases. More particularly, in the presence of sufficient iron the forming of vivianite like structures is limited by the organic phosphate and sulphide in the stream.
- the vivianite like structures that are formed are substantially formed as crystals and/or aggregates with a size substantially in the range of 10-100 ⁇ m.
- the purity of the vivianite like structures can be relatively high thereby enabling application of the structures in different processes.
- the phosphates are recovered from the separated vivianite like structures to enable use for a fertilizer production, for example.
- the vivianite like structures can be used as colour pigment, and in the production of lithium iron batteries, for example.
- the separated vivianite particles could also be recycled in the waste stream to allow further growth.
- formed (larger) vivianite particles could be separated more easily from the wastewater, for example using a separator such as an (electro)magnetic separator.
- This "growing" process is also referred to as seeding.
- other possibilities could be envisaged, such as the possibility to produce food grade phosphoric acid out of the vivianite.
- the improved removal and recovery rates of phosphates from a stream obviates or at least reduces the need for incineration of the sludge enabling recovery of phosphates and the capital investments that are associated therewith.
- the method according to the present invention does not rely on the immense use of chemicals as compared to some of the conventional processes. More particularly, the vivianite like structures are separated from the stream and the resulting concentrated stream can be subjected to a post treatment that may involve a dedicated chemical treatment. This treatment enables circular use of the iron. Also in such case a significant reduction of the use of chemicals is achieved.
- the vivianite like structures comprise more than 70%, preferably more than 80%, and most preferably about 90% or even more, of the initial amount of phosphate of the incoming stream. This further improves the efficiency of the removal and/or recovery of phosphate from a stream. Measurements with the method according to the invention even show that more than 80%, such as about 90%, of the total amount of phosphate in a sewage sludge is bound in vivianite. This significantly improves the recovery efficiencies of phosphate as compared to traditional struvite technologies, for example.
- Iron salts are also referred to as Fe (II)/FE (III) salts.
- the iron salts that are added to the stream comprise one or more of iron chloride and iron sulphate.
- the step of dosing iron salt to the stream comprises adding an amount of iron with a molar ratio of iron to phosphorus of at least 1.3, preferably at least 1.5.
- the iron chloride may include ferric and/or ferrous chloride.
- the presently preferred range is from 1.3 to 1.9, with the actual value more preferably being about 1.5.
- some additional iron salt is added to the stream to bind sulphide in the incoming stream before actually binding the phosphate in the stream.
- the amount of sulphide and/or phosphate is known to improve the effective dosing of iron salts and to prevent underdosing and/or overdosing. This may further improve the efficiency of the phosphate removal and/or phosphate recovery.
- the relatively high amount of dosed iron salts as compared to conventional treatment plants enables not only removal of phosphate it also enables effective recovery of phosphate.
- the dosing of iron salt is controlled by a (dosing) controller in response to a measurement of the initial amount of phosphate in the incoming stream.
- a dedicated dosing of the iron salt to the stream can be achieved. This prevents underdosing and/or overdosing thereby improving the overall efficiency.
- other measurements could be envisaged, such as measuring after an anaerobic stage.
- total iron (Fe) and total phosphorus (P) can be measured. Then, in response to the measurement(s), the iron dosing is adjusted to reach the desired Fe:P ratio in the sludge that was mentioned earlier for optimal P recovery. This optimal ratio is preferably somewhere between 1.3 and 1.9. In (commercial) applications this could be monitored about once /week or other time intervals. In practice, it could be that the amount of organic phosphorus is for some reason extraordinary high.
- separating the vivianite like structures from the stream comprises magnetic separating of the structures with a magnetic and/or electromagnetic separator.
- a magnetic and/or electromagnetic separator achieves an efficient and effective separation of the vivianite like structures from the stream.
- Such separator may involve a channel around which the magnets or electromagnets are provided that attract the vivianite like structures, while other non-magnetic material continues to travel through the channel such that the magnetically separated material is separated from the non-magnetic material.
- this may include the use of profiled plates, walls or surfaces, as are known components of high-gradient magnetic separators, such as the Jones separator, for example. This enables an effective and efficient separation of the magnetic vivianite like structures from the stream.
- vivianite like structures are separated from the stream with a gravity separator that separates heavy materials with a high density from light materials with a low density.
- Such gravity separator may relate to a (hydro)cyclone, for example.
- the step of recovering the phosphates, and possibly the iron, from the separated vivianite like structures comprises treating the vivianite like structures to produce iron oxide precipitates.
- the vivianite-like particles are concentrated from the stream by magnetic separation and/or gravity separation following a process step that frees (liberates) the vivianite-like particles from organic particles, such as fibers, that stick to the vivianite-like particles or entangle them.
- organic particles such as fibers
- intense shear of the liquid phase by high-speed rotors or jets will promote liberation of particles of different types that are embedded in the liquid.
- Liberation of the vivianite-like particles from organic particles in turn, will promote the effectiveness of subsequent magnetic and/or gravity separation.
- treating the vivianite like structures involves performing an alkaline treatment.
- This alkaline treatment may involve the use of sodium hydroxide (caustic soda, potassium hydroxide (caustic potash).
- the alkaline treatment involves adding potassium hydroxide that enables production of a potassium phosphate solution.
- Such recovery of phosphate involving the alkaline treatment enables an effective recovery that enables effective re-use of the phosphate and potassium in the potassium phosphate solution that can be applied as a fertilizer, for example.
- the method further comprises the step of treating the iron oxide with hydrochloric acid to produce iron chloride.
- the produced iron oxide may react with the hydrochloric acid to produce the iron chloride.
- this production of iron chloride enables a recycling step of the resulting iron chloride to the dosing step of iron salt to the stream. This improves the overall efficiency of the method for phosphate recovery by recycling the iron in the method.
- the iron oxide can be used as such in other (existing) processes, for instance as an alternative to iron ore.
- the incoming stream is a flow to an anaerobic treatment system, such as a digester.
- an anaerobic treatment system such as a digester.
- the iron is added to the sludge in the reactor and reacts to form vivianite in the digester.
- the advantage is that this will allow to start with sludge containing a low concentration of recoverable material.
- the stream as such exist of sewage sludge and/or industrial sludge and/or any other type of sludge.
- the advantage of this process is that it is not limited to a specific type of sludge. This improves the overall process efficiency.
- the pH of the stream as such is in the range of 6 - 10, preferably in the range of 6 - 9, more preferably in the range of 7 - 8.
- the advantage of a broad pH rang is that the stream as such does not need to be pre-treated. The effect is that fewer chemicals are required and that the overall process improves in efficiency. Surprisingly the method performs above expectations in the pH range of 7 - 8.
- the invention also relates to a system for phosphate recovery from a stream, the system being capable of performing the method in one or more of the embodiments according the invention, wherein the system comprising:
- system provides the same effects and advantages as those described for the method.
- system further comprises:
- the system enables an efficient and effective phosphate recovery from a stream involving a separator, such as a magnetic/electromagnetic separator and/or a gravity separator.
- the treatment system may enable performing different treatment steps, preferably including the alkaline treatment.
- the system further comprises a dosing controller and a phosphate measurement system that are configured to control dosing of iron salt in response to a measurement of the initial amount of phosphate in the incoming stream, for example.
- a dosing controller and a phosphate measurement system that are configured to control dosing of iron salt in response to a measurement of the initial amount of phosphate in the incoming stream, for example.
- This further improves the overall efficiency of the iron salt dosing preventing underdosing and/or overdosing of iron into the stream.
- the amount of sulphide can be measured to further improve the dosing.
- other measurements can be envisaged in accordance with the present invention.
- total iron (Fe) and total phosphorus (P) can be measured.
- Process 2 starts with supply of stream 4 that comprises an amount of phosphate.
- measurement step 6 measures the amount of phosphate and/or sulphide.
- Calculation step 8 determines the optimal amount of iron or iron salt to be dosed into the stream.
- iron is added to the stream to enable forming 12 of precipitates comprising vivianite like structures.
- separation step 14 the vivianite like structure is separated and removed from the stream.
- the vivianite like structures undergo a post treatment to recover the phosphorus components, such as an alkaline treatment 16. For example, this treatment may provide a potassium phosphate solution that can be used 18 as fertilizer.
- the iron oxide precipitates can be treated 20 with hydrochloric acid resulting in recycle iron stream 22 that can be used in dosing step 10. Recycle stream 22 may even obviate the need for external iron or at least significantly reduce this need.
- Recovery system 24 ( figure 2 ) comprises reactor 26 that receives incoming stream 4. In the illustrated embodiment in reactor 26 anaerobic/anoxic conditions are maintained. From reactor 26 flow 28 is directed towards separator 30. Sludge/waste 32 leaves system 24.
- the resulting vivianite like structures 34 are provided to alkaline reactor 36 to enable posttreatment, or vivianite like structures 34 are directly applied.
- the recovered phosphate for example in the form of potassium phosphate, leaves reactor 36 in flow 38 and can be used as fertilizer, for example.
- the desired ratio is determined, the actual concentrations are measured and the desired dosage is calculated in order to dose the required and optimal amount of the iron salt to maintain and/or achieve the preferred ratio.
- sensor 50 measures the composition of the stream in reactor 26, for example the amount of phosphate.
- Measurement signal 52 is provided to controller 54 that determines control setting(s) 56 of dosing device 44. This may involve periodic sampling of the sludge, for example weekly, and analysing the sample. It will be understood that also other components can be measured with one or more of sensors 50, such as the amount of sulphide that is preferably measured in a digester.
- controller 54 also provides control settings 58 to acid dosing device 60 that provides acid, such as hydrochloric acid, to acid reactor 42.
- a sewage treatment plant reactor 26 comprises a receiving reactor (a sewage treatment plant, a waste water treatment plant) that receives the phosphate rich influent.
- a receiving reactor a sewage treatment plant, a waste water treatment plant
- phosphate poor effluent leaves the system through an exit (not shown).
- the phosphate rich effluent 28 is provided to an anaerobic digester that in the illustrated embodiment is part of reactor 26. Iron is optionally added to the receiving reactor and/or the anaerobic digester.
- iron may be added before the anaerobic stage to reach the preferred Fe:P range to further reduce the downflow Phosphorus level(s).
- Separator 30 ( figure 3 ) comprises frame or housing 62 that is preferable made of steel or another magnetisable material for guiding the magnetic flux, first magnet 64 and, advantageously, second magnet 66. Magnets 64, 66, are provided at a distance wherein assembly 68 is provided. Assembly 68 comprises first (magnetisable) plate 70 and second plate 72 that in the illustrated embodiment are provided with profile 74. In the illustrated embodiment the serrated profile 74 has a height H of about 1-2 mm and a width W of about 3-4 mm. Plates 70, 72 are provided at distance D in the range of 0.1-1 mm, preferably in the range of 0.2-0.4 mm. It will be understood that another configuration for separator 30 and/or other separator techniques can be applied in accordance with the invention.
- the method according to the invention is applied to difference incoming streams with different characteristics/composition.
- the sludge remains under anaerobic or anoxic conditions for several days, for example for about 20-30 days.
- the amount of vivianite like structures has been determined by Mössbauer Spectroscopy and semi quantitative XRD measurements.
- the table illustrates that the vivianite bound phosphorus increases with the molar Fe:P in the sludge. For example, a molar ratio of about 1.11 results in more than 60% of the incoming phosphorus being bound in vivianite, while higher percentages of above 80% are measured at higher ratio's. This indicates an effective and efficient removal/recovery of phosphorus from a stream. Results are shown in table 1.
- Table 1 shows that the fraction of the phosphate present as vivianite, after digestion, depends on the molar ratio between iron and phosphate in the waste activated sludge, and thus on the amount of iron that was added in the activated sludge plant prior to anaerobic digestion.
- the digested sludge was then fed into a magnetic separator to separate the magnetic vivianite-like structures from the rest of the digested sludge (largely organics).
- Table 3 and 4 show the fraction of phosphate recovered by the magnetic separation versus the total amount of phosphate in the digested sewage sludge.
- Table 1 Percentage of phosphate present as vivianite or vivianite-like structures in digested waste activated sludge with different Fe:P ratio Sample reference Molar ratio Fe:P XRD-measurement (%) Mössbauer-measurement (%) Sludge sample 1 0.14 0 Sludge sample 2 0.50 15.3 13 Sludge sample 3 0.82 49.7 30 Sludge sample 4 1.11 63.7 Sludge sample 5 1.62 82.1 Sludge sample 6 1.57 83.6 61 Sludge sample 7 2.36 102.3 89
- the vivianite like structures are separated by a separator ( figure 3 ).
- This separator has six channels with a radius of about 1.3 mm and a length of 40 mm with a cavity volume of about 0.41 cm 3 .
- the stream has a viscosity of about 0.003 Pa.s, an estimated vivianite susceptibility of 1.0 ⁇ 10 -7 m 3 /kg, and a vivianite density of about 2300 kg/m 3 .
- the magnetic field intensity in the cavity was about 1 ⁇ 10 +06 A/m with a field gradient of about 500 T/m.
- Table 3 Percentage of phosphate present as viviante or vivianite-like structures and percentage of dry weight made up of Volatile Solids (VS), for 3 different digested waste activated sludge's that differ in molar Fe:P ratio NL Ger Fin Initial VS (%) 58.9 56.0 58.7 Vivianite P (% of total P) ⁇ 65 ⁇ 80 ⁇ 90 Molar Fe:P 1.1 1.57 2.36
- Table 4 Percentage of the iron and phosphate in digested waste activated sludge that is recovered from the bulk sludge in a magnetic separator (e.g.
- Results show that the concentration of the various materials which can be recovered does not limit the output. Low as well as high concentrations of iron and phosphor can be used.
- the iron (Fe) recovery for Finnish sludge was at 4 mL/min 53%, at 8 mL/min 49%, at 16 mL/min 31% and at 20 mL/min 31%.
- the phosphor (P) recovery for Finnish sludge was at 4 mL/min 53%, at 8 mL/min 51%, at 16 mL/min 39% and at 20 mL/min 37%.
- the enrichment increases with the flow rate for both type of sludge and elements.
- the separation becomes more selective with the increase of the flow rate.
- Higher streams reduce the part of non and/or less magnetic material susceptible to be retained.
- the experiments show the effect of the molar Fe:P ratio on the efficiency of the removal/recovery of phosphate from the stream. Furthermore, the experiments show that an effective recovery is possible by effective separation of the vivianite like structures from the stream.
- VPHGMS vertically pulsating high gradient magnetic separator
- Table 7 Result of VPHGMS separation test.
- Feed sample Dry solids content Concentrate dry mass yield Recovery
- Feed content Concentrate content Fe P Fe P Fe P Finnish sludge 2,66% 16,0% 49,0% 56,6% 12,0% 3.0% 36,8% 10,7%
- the concentrate was studied with a scanning electron microscope (SEM) combined with energy-dispersive x-ray spectroscopy (EDX).
- SEM-EDX results indicate that the concentrate is homogeneous in composition and mostly comprise vivianite ( Figure 7, wherein needle-like crystal structures which are typical for vivianite were observed).
- vivianite has an elemental phosphorus content of 12.35%. If we assume that all the phosphorus in the concentrate is bound to vivianite as indicated by SEM-EDX, the vivianite content of the concentrate is 86.6%
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
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NL2018525A NL2018525B1 (en) | 2017-03-15 | 2017-03-15 | Method and system for phosphate recovery from a stream |
EP18716378.7A EP3596016B1 (fr) | 2017-03-15 | 2018-03-14 | Méthode et système pour la récupération de phosphate d'un effluent |
PCT/NL2018/050159 WO2018169395A1 (fr) | 2017-03-15 | 2018-03-14 | Procédé et système de récupération de phosphate à partir d'un flux |
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EP18716378.7A Division EP3596016B1 (fr) | 2017-03-15 | 2018-03-14 | Méthode et système pour la récupération de phosphate d'un effluent |
EP18716378.7A Division-Into EP3596016B1 (fr) | 2017-03-15 | 2018-03-14 | Méthode et système pour la récupération de phosphate d'un effluent |
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CN110066082B (zh) * | 2019-04-16 | 2020-10-20 | 浙江大学 | 一种同步强化产酸与除磷的污泥厌氧发酵处理方法 |
NL2023428B1 (en) | 2019-07-03 | 2021-02-02 | Univ Delft Tech | Separating phosphate from treated sewer sludge |
CN111792636B (zh) * | 2020-07-29 | 2022-04-05 | 同济大学 | 一种从污泥焚烧灰中回收蓝铁矿的方法 |
CN111875023B (zh) * | 2020-08-04 | 2021-12-14 | 中国科学技术大学 | 一种去除水体中磷酸盐和有机大分子的方法 |
CN112340827A (zh) * | 2020-09-28 | 2021-02-09 | 鞍钢贝克吉利尼水处理有限公司 | 一种以酸再生含硅泥饼为原料的除磷剂及其制备方法 |
CN112661266B (zh) * | 2020-11-30 | 2023-04-25 | 苏州科技大学 | 一种利用生物膜法富集磷及回收蓝铁矿的工艺 |
CN112645447B (zh) * | 2020-11-30 | 2023-04-14 | 苏州科技大学 | 一种从含磷废水中回收蓝铁矿的系统及其工艺 |
CN113003735A (zh) * | 2021-03-17 | 2021-06-22 | 北京泷涛环境修复有限公司 | 一种间歇性曝气式地下水氨氮、有机污染生物的修复方法 |
CN114014438A (zh) * | 2021-06-18 | 2022-02-08 | 天津大学 | 一种基于管网蓝铁石捕获器的污水磷回收方法 |
EP4122895A1 (fr) * | 2021-07-13 | 2023-01-25 | OASE GmbH | Procédé de traitement des eaux, des sols, des sédiments et/ou des boues |
CN113651438A (zh) * | 2021-09-22 | 2021-11-16 | 中国科学院烟台海岸带研究所 | 一种从污泥或底泥中回收磷的方法 |
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EP2666759A1 (fr) * | 2012-05-24 | 2013-11-27 | Fertiberia, S.A. | Procédé d'obtention de phosphate ferreux à partir de déchets |
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CN104761114B (zh) * | 2014-01-07 | 2017-02-08 | 北京林业大学 | 一种污水强化除磷方法 |
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- 2018-03-14 EP EP23166436.8A patent/EP4219411A1/fr active Pending
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EP3596016B1 (fr) | 2023-09-06 |
EP3596016A1 (fr) | 2020-01-22 |
CA3056058A1 (fr) | 2018-09-20 |
ES2963634T3 (es) | 2024-04-01 |
CN110691758A (zh) | 2020-01-14 |
WO2018169395A1 (fr) | 2018-09-20 |
EP3596016C0 (fr) | 2023-09-06 |
CN110691758B (zh) | 2023-04-04 |
US11834355B2 (en) | 2023-12-05 |
US20200010342A1 (en) | 2020-01-09 |
NL2018525B1 (en) | 2018-09-24 |
PL3596016T3 (pl) | 2024-02-26 |
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